Disazo compounds containing an N,N-bis(2-amino-benzoyl)piperazine derivative as the diazo component

ABSTRACT

Sulfo-free compounds of the formula ##STR1## where R is hydrogen or C 1  -C 4  -alkyl and 
     K 1  and K 2  independently of one another are a radical of a coupling component, and the rings A and B may furthermore be monosubstituted or polysubstituted by fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, ethyl, acetyl, benzoyl, a carboxylic ester group, unsubstituted or substituted carbamyl or sulfamyl, an aryl sulfonate group, C 1  -C 4  -alkylsulfonyl, unsubstituted or substituted phenylsulfonyl, cyano or acylamino or a fused ring, are very useful as pigments for coloring printing inks, surface coatings or plastics.

The present invention relates to sulfo-free compounds of the general formula I ##STR2## where

R is hydrogen or C₁ -C₄ -alkyl and

K¹ and K² independently of one another are a radical of a coupling component, and the rings A and B may furthermore be monosubstituted or polysubstituted by fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, ethyl, acetyl, benzoyl, a carboxylic ester group, unsubstituted or substituted carbamyl or sulfamyl, an aryl sulfonate group, C₁ -C₄ -alkylsulfonyl, unsubstituted or substituted phenylsulfonyl, cyano or acylamino or a fused ring.

Specific examples of substituents for rings A and B, in addition to those stated above are COOCH₃, COOC₂ H₅, COOC₃ H₇, COOCH(CH₃)₂, COOC₄ H₉, COOC₆ H₅, COOC₆ H₁₃, COOC₈ H₁₇, COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOCH₂ C₆ H₅, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₃ H₇, CONHC₄ H₉, CONHCH(CH₃)₂, CONHCH₂ C₆ H₅, CONHC₆ H₅, CONHC₆ H₄ Cl, CONHC₆ H₃ Cl₂, CONHC₆ H₂ Cl₃, CONHC₆ H₄ Br, CONHC₆ H₄ OCH₃, CONHC₆ H₄ CH₃, CONHC₆ H₄ OC₂ H₅, CONHC₆ H₃ Cl(OCH₃), CONHC₆ H₄ NHCOCH₃, CONHC₆ H₄ NHCOC₆ H₅, CONHNHCOC₆ H₅, CONHNHCOC₆ H₄ Cl, CONHNHCOC₆ H₄ CH₃, SO₂ NH₂, SO₂ NHCH₃, SO₂ NHC₂ H₅, SO₂ NHC₃ H₇, SO₂ NHC₄ H₉, SO₂ NHCH(CH₃)₂, SO₂ NHCH₂ C₆ H₅, SO₂ NHC₆ H₅, SO₂ NHC₆ H₄ Cl, SO₂ NHC₆ H₃ Cl₂, SO₂ NHC₆ H₂ Cl₃, SO₂ NHC₆ H₄ Br, SO₂ NHC₆ H₄ OCH₃, SO₂ NHC₆ H₄ CH₃, SO₂ NHC₆ H₄ OC₂ H₅, SO₂ NHC₆ H₃ Cl(OCH₃), SO₂ NHC₆ H₄ NHCOCH₃, SO₂ NHC₆ H₄ NHCOC₆ H₅, SO₂ NHNHCOC₆ H₅, SO₂ NHNHCOC₆ H₄ Cl, SO₂ NHNHCOC₆ H₄ CH₃, SO₂ OC₆ H₅, SO₂ OC₆ H₄ CH₃, SO₂ OC₆ H₄ Cl, SO₂ OC₆ H₄ Br, SO₂ OC₆ H₄ OCH₃, SO₂ OC₆ H₄ NHCOCH₃, SO₂ OC₆ H₃ Cl₂, SO₂ CH₃, SO₂ C₂ H₅, SO₂ C₆ H₅, SO₂ C₆ H₄ Cl, NHCOCH₃, NHCOC₂ H₅, NHCOC₆ H₅, NHCONH₂, NHCON(CH₃)₂ and NHCONHC₆ H₅.

Examples of suitable coupling components K¹ H and K² H are compounds of the phenol, naphthol, acetoacetarylide, pyrazolone, quinolone, pyridine, pyrimidine, isoquinoline and pyrazolo[5,1-b]quinazolone series. Apart from phenol, o-, m- and p-cresol, 1-naphthol, 2-naphthol and resorcinol, these compounds are essentially of the formulae: ##STR3## where R¹ is C₁ -C₄ -alkoxy, unsubstituted or substituted phenoxy or unsubstituted or substituted arylamino,

R² is unsubstituted or substituted aryl,

R³ is hydrogen, methyl, carboxyl, C₁ -C₈ -alkoxycarbonyl, unsubstituted or substituted carbamyl or the substituents stated for R²,

R⁴ is hydrogen or the substituents stated for R²,

R⁵ is hydrogen or C₁ -C₁₃ -alkyl,

R⁶ is hydrogen, hydroxyl, unsubstituted or substituted amino or C₁ -C₄ -alkyl,

R⁷ is hydrogen, cyano, carbamyl, acetyl or benzoyl,

R⁸ and R¹³ independently of one another are each hydrogen or unsubstituted or substituted alkyl, cycloalkyl, phenyl or benzyl,

R⁹, R¹⁰ and R¹¹ independently of one another are each hydrogen or unsubstituted or substituted alkyl, cycloalkyl or phenyl, or R¹⁰ and R¹¹ together with the nitrogen may furthermore form a 5-membered or 6-membered heterocyclic ring,

R¹² and R¹⁷ independently of one another are each oxygen, amino or cyanoimino,

R¹⁴ is a radical R⁸, amino or acylamino,

R¹⁵ is hydrogen or unsubstituted or substituted phenyl and

R¹⁶ is hydroxyl, methyl, a carboxylic ester group or unsubstituted or substituted aryl or acylamino, and the ring A may be substituted in the stated manner.

Specific examples of the radicals R¹ to R¹⁶, in addition to those listed above are the following substituents:

R¹ is OCH₃, OC₂ H₅, OC₆ H₅, OC₆ H₄ Cl, OC₆ H₃ Cl₂, NHC₆ H₅, NHC₆ H₄ Cl, NHC₆ H₃ Cl₂, NHC₆ H₂ Cl₃, NHC₆ H₃ Cl(CH₃), NHC₆ H₄ CH₃, NHC₆ H₄ C₂ H₅, NHC₆ H₃ (OCH₃)₂, NHC₆ H₃ (CH₃)(OCH₃), NHC₆ H₃ (CH₃)₂, NHC₆ H₂ (OCH₃)₂ Cl, NHC₆ H₂ (OCH₃)(CH₃)Cl, NHC₆ H₃ Cl(OCH₃), NHC₆ H₄ NHCOCH₃, NHC₆ H₄ NHCOC₆ H₅, NHC₆ H₄ OC₂ H₅, ##STR4## or NHC₆ H₃ (OC₂ H₅)₂ ; R² is C₆ H₅, C₆ H₄ Cl, C₆ H₄ CH₃, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, C₆ H₄ NHCOCH₃, C₆ H₄ NHCOC₆ H₅, C₆ H₃ Cl₂, C₆ H₃ (CH₃)₂, C₆ H₃ (OCH₃)₂, C₆ H₃ (OC₂ H₅)₂, C₆ H₃ Cl(CH₃), C₆ H₃ Cl(OCH₃), C₆ H₃ (CH₃)(OCH₃), C₆ H₂ Cl₃, C₆ H₂ (OCH₃)₂ Cl, C₆ H₂ (OCH₃)Cl(CH₃), ##STR5## C₆ H₄ NO₂, C₆ H₄ COCH₃ or C₆ H₄ COC₆ H₅ ;

R³ is COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₃ H₇ or CONHC₄ H₉ ;

R⁵ is CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₁₃, C₈ H₁₇, C₁₂ H₂₅ or C₁₃ H₂₇ ;

R⁶ is CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁ α-ethylphenyl, phenyl, methylphenyl or chlorophenyl;

R⁸ and R¹³ are each methyl, ethyl, propyl, butyl, β-hydroxyethyl, β-methoxyethyl, γ-methoxypropyl, β-cyanoethyl, β-carbomethoxyethyl, β-carboethoxyethyl, β-acetoxyethyl, β-ethoxycarbonylethyl, γ-acetylaminopropyl, phenoxycarbonyloxyethyl, phenylaminocarbonyloxyethyl, butylaminocarbonyloxyethyl, benzyl, β-phenethyl, phenyl, dichlorophenyl, trichlorophenyl, acetylaminophenyl, carboxyphenyl, cyanophenyl, chlorophenyl, sulfoethyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, methylphenyl, dimethylphenyl, methylchlorophenyl, methoxyphenyl, heptyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, oleyl or other radicals of industrial fatty amines, such as coconut fatty amine or tallow fatty amine or their hydrogenation products; other examples are amino-substituted alkyl radicals, such as C₁ -C₁₈ -mono- or dialkylamino-substituted alkyl, cycloalkylaminoalkyl, aralkylaminoalkyl, or alkyl substituted by a N-heterocylic structure, and these aminoalkyl radicals may furthermore be quaternary radicals. Alkyl is preferably of 2 or 3 carbon atoms, ie. of the formula c₂ H₄ or, in particular, C₃ H₆. Specific examples of radicals are ##STR6## R⁹, R¹⁰ and R¹¹ are each alkyl of 1 to 8 carbon atoms, C₂ -C₆ -alkyl which is substituted by hydroxyl, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy, phenoxyethoxy or benzyloxy, or cyclohexyl, benzyl, phenylethyl, phenylhydroxyethyl, phenylpropyl or phenylbutyl, or phenyl which is unsubstituted or substituted by chlorine, methyl, methoxy or ethoxy, or polyalkoxyalkyl, hydroxypolyalkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonylalkyl, alkanoyl, aralkanoyl, aroyl, alkylsulfonyl or arylsulfonyl, for example the radicals stated in U.S. Pat. No. 3,998,802;

R¹⁴ is C₁ -C₈ -alkanoylamino or is benzoylamino which is unsubstituted or monosubstituted or disubstituted by hydroxyl, chlorine, methyl, methoxy, acetylamino, nitro or amino;

R¹⁵ is phenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, methoxyphenyl, methylphenyl or dimethylphenyl;

R¹⁶ is COOCH₃, COOC₂ H₅, phenyl, the radicals stated for R¹⁵, NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCONH₂, NHCONHC₆ H₅ or NHCOCONHC₆ H₅ ;

Other examples of suitable coupling components are 4-hydroxycoumarin, 2-acetonylbenzothiazole, 2-cyanomethylbenzpothiazole, 2-cyanomethylbenzimidazole, 2-cyanomethyl-4-hydroxyquinazoline, 2-hydroxyquinoxaline, 2-carbamylbenzimidazole, 2-acetonylbenzimidazole, 2-phenyl-4-amino-6-hydroxypyrimidine, 4-carbamyl-2,6-dihydroxypyrimidine, 2,4dihydroxypyrimido[1,2-a]benzimidazole, 4-amino-2-hydroxypyrimido[1,2-a]benzimidazole, 2H-pyrimido[2,1-b]benzothiazole-2,4-(3H)-dione, 1,4-(bisacetoacetamino)benzene and 4,'-bis-(acetoacetamino)-3,3'-dimethyldiphenyl.

Of particular importance are compounds of the formula Ia ##STR7## where K³ and K⁴ independently of one another are each a radical of a coupling component of the acetoacetarylide, pyrazolone, quinolone, pyrimidine, isoquinolone or pyrazolo[5,1-b]quinazolone series or of 2-naphthol and in particular a radical of the pyridine or 2-naphthol-3-carboxylic acid arylamide series, and the phenylene radicals A may be monosubstituted or polysubstituted by chlorine, bromine or nitro, the substituents being identical or different in the case of polysubstitution.

R¹ is preferably NHC₆ H₅ which is unsubstituted or monosubstituted or polysubstituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl or sulfamyl, the substituents being identical or different in the case of polysubstitution, or is preferably ##STR8## R² is preferably phenyl which is unsubstituted or monosubstituted or polysubstituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl or sulfamyl, the substituents being identical or different in the case of polysubstitution,

R³ is preferably hydrogen, methyl, C₁ -C₄ -alkoxycarbonyl, carbamyl, C₁ -C₄ -alkylaminocarbonyl or the radicals preferred for R²,

R⁴ is preferably hydrogen or the radicals preferred for R²,

R⁵ is preferably hydrogen or C₁ -C₈ -alkyl,

R⁶ is preferably hydrogen, methyl, hydroxyl or amino,

R⁷ is preferably hydrogen, cyano, carbamyl, acetyl or benzoyl,

R⁸ and R¹³ independently of one another are each preferably hydrogen, alkyl, alkenyl, cycloalkyl, benzyl or a radical R²,

R⁹, R¹⁰ and R¹¹ independently of one another are each preferably hydrogen, alkyl, cycloalkyl, benzyl or a radical R², and R¹⁰ and R¹¹ together with the nitrogen may furthermore form a 5-membered or 6-membered ring,

R¹² and R¹⁷ independently of one another are each preferably oxygen, imino or cyanoimino,

R¹⁴ is preferably a radical R⁸ or acylamino,

R¹⁵ is preferably hydrogen or a radical R² and

R¹⁶ is preferably methyl or a radical R².

The compounds of the formula (I) can be prepared by reacting a bisdiazonium compound of an amine of the formula (II) ##STR9## with coupling components HK¹ and HK², where HK¹ and HK² may be identical or different.

The coupling products (I) are as a rule pigments. They are not always obtained in the optimum physical form for the intended use. However, they may be converted to a suitable pigmentary form by a conventional method, such as milling, in the presence or absence of salts or liquids, or heating in aqueous suspension at a suitable pH or in a solvent.

Another possible method of improving the performance characteristics of the pigments is the known procedure of coating the pigments with compounds which preferably have a similar structure. For the preparation of the coating agent, it is generally advantageous to use the same diazo component and to vary the coupling component. In this case, a mixture of coupling components can be used from the outset for the pigment preparation, the coupling component which leads to the coating agent being added in appropriately small amounts, or the coating agent is synthesized separately and added to the pigmentat a later stage.

For the preparation of printing inks using pigments of the formula (I), it may be advantageous to improve the distribution properties of the pigments in the printing ink by prior coating with resins. Coating may be effected simultaneously with coupling, after coupling or after conditioning.

Some of the pigments of the formula (I) possess good color strength, fastness to overcoating and fastness to migration and are therefore suitable for the preparation of printing inks and surface coatings and for coloring plastics.

The Examples which follow illustrate the preparation and use of compounds of the formula (I). In the Examples, parts and percentages are by weight, unless stated otherwise.

Below, the radical ##STR10## is abbreviated to DIAP<, and substituted radicals are named correspondingly, eg. (5,5'-dibromo DIAP)<.

Examples EXAMPLE 1

32.4 parts of dianthranilic acid piperazide in 330 parts of water and 170 parts of ice are stirred, 70 parts by volume of concentrated hydrochloric acid are added and diazotization is carried out at room temperature with 64 parts by volume of 23% strength aqueous sodium nitrite solution. After 3 hours, the excess nitrite is destroyed with amidosulfonic acid. The diazotized compound is then gradually added, at 0° C., to a solution of 53.6 parts of N-(2,5-dimethoxy-4-chlorophenyl)-acetoacetamide in 600 parts of water, the said amide initially being dissolved under alkaline conditions and the solution then being brought to pH 6 with hydrochloric acid. Coupling is completed at room temperature at pH 6, and the pigment is filtered off under suction and washed with hot water. Thereafter, it is stirred in fresh water, stirred for 4 hours at pH 10 and 98° C., filtered off under suction, washed and dried. 80 parts of a yellow pigment are obtained, the compound being of the formula ##STR11##

EXAMPLE 2

16.2 parts of dianthranilic acid piperazide in 200 parts of water are stirred, 60 parts by volume of concentrated hydrochloric acid are added dropwise and diazotization is effected at 5° C. with 64 parts by volume of 23% strength aqueous sodium nitrite solution. Stirring is continued at room temperature until a clear solution is formed, the excess nitrite is destroyed with amidosulfonic acid, the solution is filtered, cooled to 0° C. and buffered at pH 2.5 with sodium acetate, and the coupling component prepared as described below is run in. 50 parts of 2-hydroxynaphthalene-3-carboxylic acid N-phenylamide and 1.4 parts of 2-naphthol are dissolved in 50 parts of N-methylpyrrolidone, 32 parts of 50 percent strengthsodium hydroxide solution and 500 parts of water at 45° C., and the solution is cooled to room temperature. Coupling is completed at 20° C. and the product is filtered off under suction and washed with water. The filter cake is stirred in water and brought to pH 10 with sodium carbonate, and 200 parts of a 10 percent strength aqueous rosin solution which has been rendered alkaline with sodium hydroxide are added. The mixture is stirred for 4 hours at 95° C., brought back to pH 7, kept at 95° C. for a further 2 hours and cooled to 60° C., and the product is filtered off under suction, washed with water and dried at 60° C. 103 g of red pigment are obtained. The principal component is of the formula ##STR12## and the important secondary component is of the formula ##STR13##

EXAMPLE 3

101 parts of dianthranilic acid piperazide in 600 parts of water are stirred with the addition of 0.6 part of the sodium salt of an alkylnaphthalenesulfonic acid. 180 parts by volume of concentrated hydrochloric acid are added, after which stirring is continued for 1 hour. Diazotization is carried out at 5° C. with 180 parts by volume of a 23 percent strength aqueous solution of sodium nitrite. The temperature is allowed to increase to 20° C. in the course of 3 hours, excess nitrite is destroyed with amidosulfonic acid, and the solution is run into a suspension of the coupling component, the suspension being prepared as described below. 104.4 parts of 3-methyl-1-phenylpyrazol-5-one are dissolved in 600 parts of water and 360 parts of 2N sodium hydroxide solution, the solution is cooled to 0° C. and precipitated with 1:1 glacial acetic acid/water, and 208 parts of a 10 percent strength rosin solution are then added, the said solution having been rendered alkaline with sodium hydroxide. Coupling is completed by bringing the pH to 4 by adding sodium acetate. The mixture is stirred overnight, after which it is filtered under suction and the residue is washed. The moist press cake is introduced into water, brought to pH 1.2 with dilute hydrochloric acid and stirred for 4 hours at 95° C. Filtration under suction, washing and drying in an oven at 60° C. give 272 parts of yellow pigment. The compound is of the formula ##STR14##

EXAMPLE 4

32.4 parts of dianthranilic acid piperazide in 120 parts of water are stirred with the addition of 0.2 part of the sodium salt of alkylnaphthalenesulfonic acid. After the addition of 50 parts by volume of 30 percent strength hydrochloric acid, a solution is formed for a short time and the hydrochloride is then precipitated. The mixture is cooled to 5° C., after which diazotization is carried out using 60 parts by volume of 23 percent strength aqueous sodium nitrite solution. Stirring is continued for 2 hours at room temperature, and the excess nitrite is destroyed with amidosulfonic acid. After filtration to effect clarification, a mixture of a solution of 30 parts of 3-cyano-2,6-dihydroxy-4-methylpyridine in 100 parts by volume of 2N sodium hydroxide solution, 600 parts by volume of water and 650 parts of a 10 percent strength aqueous alkaline rosin solution is added dropwise. Thereafter, the mixture is heated at 90° C. for three hours and the product is filtered off under suction, washed neutral with water and dried at 60° C. to give 123 g of a yellow pigment. The compound is of the formula ##STR15##

EXAMPLE 5

44 parts of dianthranilic acid piperazide in 150 parts of water are stirred with the addition of 0.2 part of the sodium salt of an alkylnaphthalenesulfonic acid. 150 parts by volume of concentrated hydrochloric acid are added, after which stirring is continued for one hour. The mixture is cooled to 5° C. and diazotization is then carried out using 81 parts by volume of a 23 percent strength aqueous sodium nitrite solution. Excess nitrite is destroyed with amidosulfonic acid. 63 parts of 3-cyano-N-hexyl-6-hydroxy-4-methylpyrid-2-one are dissolved in 750 parts of water with the addition of NaOH at 50° C., and the solution is filtered. This solution is cooled to room temperature, after which the diazonium salt solution is run in, the latter solution having been clarified by filtration. Stirring is continued for one hour at 50° C. and for one hour at 95° C., after which the product is filtered off under suction, washed neutral with hot water and dried at 70° C. to give 109 parts of a yellow pigment. The compound is of the formula ##STR16##

EXAMPLE 6

32.4 parts of dianthranilic acid piperazide in 120 parts of water are stirred with the addition of 0.2 part of the sodium salt of an alkylnaphthalenesulfonic acid. 75 parts by volume of concentrated hydrochloric acid are added, after which stirring is continued for one hour. Diazotization is carried out at room temperature with 64 parts by volume of a 23 percent strength aqueous sodium nitrite solution, after which excess nitrite is destroyed with amidosulfonic acid. 39 parts of N-butyl-3-cyano-6-hydroxy-4-methylpyrid-2-one and 1.6 parts of 3-cyano-2,6-dihydroxy-4-methylpyridine are dissolved in 300 parts of water with 8 parts of NaOH, and the solution is mixed with 152 parts of a 10 percent strength aqueous rosin solution. The diazonium salt solution is filtered into the mixture. Stirring is continued for half an hour, after which the pH is brought to 1.2, the mixture is stirred for 4 hours at 95° C. and the product is then filtered off under suction, washed and dried at 40° C. to give 92.5 parts of a yellow pigment. The principal component is of the formula ##STR17## and the important secondary component is of the formula ##STR18##

EXAMPLE 7

172 parts of piperazine and 968 parts of 5-bromoisatoic anhydride in 2000 parts of dioxane are stirred under reflux for 3 hours. The suspension is diluted with 500 parts of ethanol and filtered under suction, the filter cake is washed with ethanol and then with water and is then stirred in 2800 parts of 10 percent strength hydrochloric acid for 4 hours at 95° C. The product is filtered off under suction, washed neutral and dried at 70° C. Yield: 631 parts, bromine content: 31.6%.

53.6 parts of the resulting diazo component are boiled up in 500 parts of glacial acetic acid, the mixture is cooled to 5° C. and 58 parts of nitrosylsulfuric acid are then added dropwise. Stirring is continued for 3 hours at room temperature, the mixture is precipitated on ice, excess nitrite is destroyed by adding urea, and the mixture is run into the coupling component, which is prepared as prepared below. 15 parts of 2,6-dihydroxy-3-cyano-4-methylpyridine are dissolved in water which has been rendered alkaline, and precipitated at 0° C. by adding dilute hydrochloric acid. Coupling is carried out at 0° C. and pH 6. The pigment is filtered off under suction, washed, stirred in water at pH 10 for 4 hours at 98° C., filtered off under suction, washed neutral and dried to give 80 parts of a yellow pigment. The compound is of the formula ##STR19##

The other colorants may also be prepared by processes similar to those described:

    ______________________________________                                          ##STR20##                                                                     Example No.                                                                              R.sup.1               Color                                          ______________________________________                                         8         OCH.sub.3             red                                            9         OC.sub.2 H.sub.5      red                                            10                                                                                        ##STR21##            red                                            11                                                                                        ##STR22##            red                                            12                                                                                        ##STR23##            red                                            13                                                                                        ##STR24##            red                                            14                                                                                        ##STR25##            red                                            15                                                                                        ##STR26##            red                                            16                                                                                        ##STR27##            red                                            17                                                                                        ##STR28##            red                                            18                                                                                        ##STR29##            red                                            19                                                                                        ##STR30##            red                                            20                                                                                        ##STR31##            red                                            21                                                                                        ##STR32##            red                                            22                                                                                        ##STR33##            red                                            23                                                                                        ##STR34##            red                                            24                                                                                        ##STR35##            red                                            25                                                                                        ##STR36##            red                                            26                                                                                        ##STR37##            red                                            27                                                                                        ##STR38##            red                                            28                                                                                        ##STR39##            red                                            29                                                                                        ##STR40##            red                                            30                                                                                        ##STR41##            red                                            31                                                                                        ##STR42##            red                                            32                                                                                        ##STR43##            red                                            33                                                                                        ##STR44##            red                                            34                                                                                        ##STR45##            red                                            35                                                                                        ##STR46##            red                                            36                                                                                        ##STR47##            red                                            37                                                                                        ##STR48##            red                                            38                                                                                        ##STR49##            red                                            ______________________________________                                    

    ______________________________________                                          ##STR50##                                                                     Example No.                                                                              R.sup.2               Color                                          ______________________________________                                         39                                                                                        ##STR51##            yellow                                         40                                                                                        ##STR52##            yellow                                         41                                                                                        ##STR53##            yellow                                         42                                                                                        ##STR54##            yellow                                         43                                                                                        ##STR55##            yellow                                         44                                                                                        ##STR56##            yellow                                         45                                                                                        ##STR57##            yellow                                         46                                                                                        ##STR58##            yellow                                         47                                                                                        ##STR59##            yellow                                         48                                                                                        ##STR60##            yellow                                         49                                                                                        ##STR61##            yellow                                         50                                                                                        ##STR62##            yellow                                         51                                                                                        ##STR63##            yellow                                         52                                                                                        ##STR64##            yellow                                         53                                                                                        ##STR65##            yellow                                         54                                                                                        ##STR66##            yellow                                         55                                                                                        ##STR67##            yellow                                         56                                                                                        ##STR68##            yellow                                         57                                                                                        ##STR69##            yellow                                         58                                                                                        ##STR70##            yellow                                         ______________________________________                                    

    ______________________________________                                          ##STR71##                                                                     Example No.                                                                               R.sup.3        R.sup.4                                                                               Color                                         ______________________________________                                         59         NH.sub.2       H      yellow                                        60         CH.sub.3       H      yellow                                        61         C.sub.6 H.sub.5                                                                               H      yellow                                        62         C.sub.6 H.sub.5                                                                               C.sub.6 H.sub.5                                                                       yellow                                        63         CONH.sub.2     C.sub.6 H.sub.5                                                                       yellow                                        64         COOCH.sub.3    C.sub.6 H.sub.5                                                                       yellow                                        65         COOC.sub.2 H.sub.5                                                                            C.sub.6 H.sub.5                                                                       yellow                                        ______________________________________                                    

    ______________________________________                                          ##STR72##                                                                     Example No.  R.sup.4        Color                                              ______________________________________                                         66                                                                                           ##STR73##     yellow                                             67                                                                                           ##STR74##     yellow                                             68                                                                                           ##STR75##     yellow                                             69                                                                                           ##STR76##     yellow                                             70                                                                                           ##STR77##     yellow                                             71                                                                                           ##STR78##     yellow                                             72                                                                                           ##STR79##     yellow                                             73                                                                                           ##STR80##     yellow                                             74                                                                                           ##STR81##     yellow                                             75                                                                                           ##STR82##     yellow                                             76                                                                                           ##STR83##     yellow                                             77                                                                                           ##STR84##     yellow                                             78                                                                                           ##STR85##     yellow                                             79                                                                                           ##STR86##     yellow                                             80                                                                                           ##STR87##     yellow                                             81                                                                                           ##STR88##     yellow                                             82                                                                                           ##STR89##     yellow                                             ______________________________________                                    

    ______________________________________                                          ##STR90##                                                                     Example No.    R          Color                                                ______________________________________                                         83             H          yellow                                               84             4-Cl       yellow                                               85             2,4-Cl.sub.2                                                                              yellow                                               86             4-CH.sub.3 yellow                                               87             4-NO.sub.2 yellow                                               88             4-OCH.sub.3                                                                               yellow                                               89                                                                                             ##STR91## yellow                                               90                                                                                             ##STR92## yellow                                               91             2,5-(OCH.sub.3).sub.2                                                                     yellow                                               92             2,5-Cl.sub.2                                                                              yellow                                               ______________________________________                                    

    ______________________________________                                          ##STR93##                                                                     Example No.     R.sup.5   Color                                                ______________________________________                                         93              H         yellow                                               94              CH.sub.3  yellow                                               95              C.sub.2 H.sub.5                                                                          yellow                                               96              C.sub.3 H.sub.7 (n)                                                                      yellow                                               97                                                                                              ##STR94##                                                                               yellow                                               98              C.sub.4 H.sub.9 (n)                                                                      yellow                                               ______________________________________                                    

    ______________________________________                                          ##STR95##                                                                     Example No.  R.sup.8         Color                                             ______________________________________                                          99          CH.sub.3        yellow                                            100          C.sub.2 H.sub.5 yellow                                            101          C.sub.3 H.sub.7 (n)                                                                            yellow                                            102                                                                                          ##STR96##      yellow                                            103          C.sub.4 H.sub.9 (n)                                                                            yellow                                            104          CH.sub.2 CH(CH.sub.3).sub.2                                                                    yellow                                            105          CH(CH.sub.3)C.sub.2 H.sub.5                                                                    yellow                                            106          C.sub.5 H.sub.11 (n)                                                                           yellow                                            107          CH(C.sub.2 H.sub.5).sub.2                                                                      yellow                                            108          C.sub.2 H.sub.4 CH(CH.sub.3).sub.2                                                             yellow                                            109          CH.sub.2 C(CH.sub.3).sub.3                                                                     yellow                                            110                                                                                          ##STR97##      yellow                                            111          C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                              yellow                                            112                                                                                          ##STR98##      yellow                                            113                                                                                          ##STR99##      yellow                                            114                                                                                          ##STR100##     yellow                                            115                                                                                          ##STR101##     yellow                                            116                                                                                          ##STR102##     yellow                                            117                                                                                          ##STR103##     yellow                                            118          CH.sub.2C.sub.6 H.sub.5                                                                        yellow                                            119          CH(CH.sub.3)C.sub.6 H.sub.5                                                                    yellow                                            120          CH(CH.sub.3)C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                    yellow                                            121          C.sub.6 H.sub.5 yellow                                            122          C.sub.8 H.sub.17 (n)                                                                           yellow                                            123          C.sub.10 H.sub.21                                                                              yellow                                            124          C.sub.12 H.sub.25                                                                              yellow                                            125          C.sub.14 H.sub.29                                                                              yellow                                            126          C.sub.16 H.sub.33                                                                              yellow                                            127          C.sub.18 H.sub.37                                                                              yellow                                            128          C.sub.20 H.sub.41                                                                              yellow                                            129          C.sub.7 H.sub.15                                                                               yellow                                            130          C.sub.13 H.sub.17                                                                              yellow                                                         (isomer mixture)                                                  131          C.sub.9 H.sub.19                                                                               yellow                                                         (isomer mixture)                                                  132          C.sub.18 H.sub.35                                                                              yellow                                            133          C.sub.16 H.sub.31                                                                              yellow                                            134          C.sub.2 H.sub.4 OH                                                                             yellow                                            135          C.sub.2 H.sub.4 OCH.sub.3                                                                      yellow                                            136          C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                               yellow                                            137          C.sub.3 H.sub.6 OH                                                                             yellow                                            138          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OH                                                            yellow                                            139          CH.sub.2 CH(CH.sub.3)OH                                                                        yellow                                            140          C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                               yellow                                            141          CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                                 yellow                                            142          CH(CH.sub.3)CH.sub.2 OH                                                                        yellow                                            143          C.sub.3 H.sub.6 OCH.sub.3                                                                      yellow                                            144          C.sub.3 H.sub.6 OC.sub.9 H.sub.19 (iso)                                                        yellow                                            145          CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 OH                                                         yellow                                            ______________________________________                                    

    ______________________________________                                          ##STR104##                                                                    Example No.                                                                             R.sup.6  R.sup.7  R.sup.8    Color                                    ______________________________________                                         146      CH.sub.3 CONH.sub.2                                                                              H          yellow                                   147      CH.sub.3 CONH.sub.2                                                                              CH.sub.3   yellow                                   148      CH.sub.3 CONH.sub.2                                                                              C.sub.2 H.sub.5                                                                           yellow                                   149      CH.sub.3 CONH.sub.2                                                                              C.sub.3 H.sub.7 (n)                                                                       yellow                                   150      CH.sub.3 CONH.sub.2                                                                               ##STR105##                                                                               yellow                                   151      CH.sub.3 CONH.sub.2                                                                              C.sub.4 H.sub.9 (n)                                                                       yellow                                   152      CH.sub.3 CONH.sub.2                                                                               ##STR106##                                                                               yellow                                   153      CH.sub.3 CONH.sub.2                                                                               ##STR107##                                                                               yellow                                   154      CH.sub.3 CONH.sub.2                                                                              C.sub.5 H.sub.11 (n)                                                                      yellow                                   155      CH.sub.3 CONH.sub.2                                                                               ##STR108##                                                                               yellow                                   156      CH.sub.3 CONH.sub.2                                                                              C.sub.6 H.sub.13 (n)                                                                      yellow                                   157      CH.sub.3 CONH.sub.2                                                                              C.sub.8 H.sub.17 (n)                                                                      yellow                                   158      CH.sub.3 CONH.sub.2                                                                               ##STR109##                                                                               yellow                                   159      CH.sub.3 H        H          yellow                                   160      CH.sub.3 H        CH.sub.3   yellow                                   161      CH.sub.3 H        C.sub.2 H.sub.5                                                                           yellow                                   162      CH.sub.3 H        C.sub.3 H.sub.7 (n)                                                                       yellow                                   163      CH.sub.3 H                                                                                        ##STR110##                                                                               yellow                                   164      CH.sub.3 H        C.sub.4 H.sub.9 (n)                                                                       yellow                                   165      CH.sub.3 H        C.sub.6 H.sub.13                                                                          yellow                                   166      CH.sub.3 COCH.sub.3                                                                              H          yellow                                   167      CH.sub.3 COCH.sub.3                                                                              CH.sub.3   yellow                                   168      CH.sub.3 COCH.sub.3                                                                              C.sub.2 H.sub.5                                                                           yellow                                   169      CH.sub.3 COCH.sub.3                                                                              C.sub.3 H.sub.7 (n)                                                                       yellow                                   170      CH.sub.3 COCH.sub.3                                                                               ##STR111##                                                                               yellow                                   171      CH.sub. 3                                                                               COCH.sub.3                                                                              C.sub.4 H.sub.9 (n)                                                                       yellow                                   172      CH.sub.3 COCH.sub.3                                                                              C.sub.6 H.sub.13                                                                          yellow                                   173      CONH.sub.2                                                                              H        H          yellow                                   174      OH       CN       H          yellow                                   175      OH       CONH.sub.2                                                                              H          yellow                                   176      H        CN       H          yellow                                   177      H        CN       CH.sub.3   yellow                                   178      H        CN       C.sub.2 H.sub.5                                                                           yellow                                   179      H        CN       C.sub.3 H.sub.7                                                                           yellow                                   180      H        CN                                                                                       ##STR112##                                                                               yellow                                   181      H        CN       C.sub.4 H.sub.9                                                                           yellow                                   182      H        COCH.sub.3                                                                              H          yellow                                   183      H        COCH.sub.3                                                                              CH.sub.3   yellow                                   184      H        COCH.sub.3                                                                              C.sub.2 H.sub.5                                                                           yellow                                   185      H        COCH.sub.3                                                                              C.sub.3 H.sub.7                                                                           yellow                                   186      H        COCH.sub.3                                                                               ##STR113##                                                                               yellow                                   187      H        COCH.sub.3                                                                              C.sub.4 H.sub.9                                                                           yellow                                   188      H        CONH.sub.2                                                                              H          yellow                                   189      H        CONH.sub.2                                                                              CH.sub.3   yellow                                   190      H        CONH.sub.2                                                                              C.sub.2 H.sub.5                                                                           yellow                                   191      H        CONH.sub.2                                                                              C.sub.3 H.sub.7                                                                           yellow                                   192      H        CONH.sub.2                                                                               ##STR114##                                                                               yellow                                   193      H        CONH.sub.2                                                                              C.sub.4 H.sub.9                                                                           yellow                                   ______________________________________                                    

    ______________________________________                                          ##STR115##                                                                    Example No.  X          Y        Color                                         ______________________________________                                         194          HO         NH.sub.2 yellow                                        195          HO         NHCH.sub.3                                                                              yellow                                        196          NH.sub.2   NH.sub.2 orange                                        197          NHCH.sub.3 NHCH.sub.3                                                                              orange                                        198          NH.sub.2   NHCH.sub.3                                                                              orange                                        199          NHC.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.5                                                                       orange                                        200          NH.sub.2   NHC.sub.2 H.sub.5                                                                       orange                                        201          NHC.sub.6 H.sub.5                                                                         NHC.sub.6 H.sub.5                                                                       orange                                        202          NH.sub.2   NHC.sub.6 H.sub.5                                                                       orange                                        ______________________________________                                    

    ______________________________________                                          ##STR116##                                                                    Example No.                                                                             R.sup.8 R.sup.12                                                                              R.sup.13  R.sup.17                                                                             Color                                  ______________________________________                                         203      H       O      H         O     yellow                                 204      H       NH     H         O     yellow                                 205      H       NH     H         NH    yellow                                 206      H       NH     H         NCN   yellow                                 207      H       O      H         NH    yellow                                 208      H       O      CH.sub.3  O     yellow                                 209      H       O      C.sub.2 H.sub.5                                                                          O     yellow                                 210      CH.sub.3                                                                               O      CH.sub.3  O     yellow                                 211      CH.sub.3                                                                               O      C.sub.6 H.sub.5                                                                          O     yellow                                 212      C.sub.6 H.sub.5                                                                        O      C.sub.6 H.sub.5                                                                          O     yellow                                 213      H       O      C.sub.6 H.sub.5                                                                          O     yellow                                 214      CH.sub.3                                                                               O      CH.sub.3  NH    yellow                                 215      H       O                                                                                      ##STR117##                                                                              O     yellow                                 216      H       O                                                                                      ##STR118##                                                                              O     yellow                                 ______________________________________                                    

    ______________________________________                                          ##STR119##                                                                    Example No.                                                                              K.sup.1 H             Color                                          ______________________________________                                         217                                                                                       ##STR120##           red                                            218                                                                                       ##STR121##           yellow                                         219                                                                                       ##STR122##           yellow                                         220                                                                                       ##STR123##           yellow                                         221                                                                                       ##STR124##           yellow                                         222                                                                                       ##STR125##           yellow                                         223                                                                                       ##STR126##           yellow                                         224                                                                                       ##STR127##           yellow                                         ______________________________________                                    

    ______________________________________                                          ##STR128##                                                                    Example No.   R.sup.14     Color                                               ______________________________________                                         225           H            yellow                                              226           CH.sub.3     yellow                                              227           C.sub.2 H.sub.5                                                                             yellow                                              228           C.sub.3 H.sub.7                                                                             yellow                                              229                                                                                           ##STR129##  yellow                                              230           C.sub.4 H.sub.9                                                                             yellow                                              231           NHC.sub.6 H.sub.5                                                                           yellow                                              232                                                                                           ##STR130##  yellow                                              233                                                                                           ##STR131##  yellow                                              ______________________________________                                    

    ______________________________________                                          ##STR132##                                                                    Example No.   A           R.sup.16                                                                              Color                                         ______________________________________                                         234             7-Cl      CH.sub.3                                                                              yellow                                        235             7-Br      CH.sub.3                                                                              yellow                                        236           5,7-Cl.sub.2                                                                               CH.sub.3                                                                              yellow                                        237             7-Cl, 5-Br                                                                               CH.sub.3                                                                              yellow                                        238           5,7-Br.sub.2                                                                               CH.sub.3                                                                              yellow                                        239             5-Cl      CH.sub.3                                                                              yellow                                        240             7-Br, 5-Cl                                                                               CH.sub.3                                                                              yellow                                        241             8-Cl      CH.sub.3                                                                              yellow                                        242             7-Cl      C.sub.6 H.sub.5                                                                       yellow                                        243             7-Br      C.sub.6 H.sub.5                                                                       yellow                                        244             5-Cl      C.sub.6 H.sub.5                                                                       yellow                                        245           5,7-Cl.sub.2                                                                               C.sub.6 H.sub.5                                                                       yellow                                        246           5,7-Br.sub.2                                                                               C.sub.6 H.sub.5                                                                       yellow                                        247             8-Cl      C.sub.6 H.sub.5                                                                       yellow                                        248           H           CH.sub.3                                                                              yellow                                        249           H           C.sub.6 H.sub.5                                                                       yellow                                        ______________________________________                                    

    ______________________________________                                          ##STR133##                                                                    Example No.     A         Color                                                ______________________________________                                         250               5-Cl    yellow                                               251               5-Br    yellow                                               252             3,5-Cl.sub.2                                                                             yellow                                               253             3,5-Br    yellow                                               254               3-Cl, 5-Br                                                                             yellow                                               255               3-Br, 5-Cl                                                                             yellow                                               ______________________________________                                    

    ______________________________________                                          ##STR134##                                                                    Example No.                                                                               A           R.sup.8   Color                                         ______________________________________                                         256          5-Cl      H         yellow                                        257          5-Cl      CH.sub.3  yellow                                        258          5-Cl      C.sub.2 H.sub.5                                                                          yellow                                        259          5-Cl      C.sub.3 H.sub.7                                                                          yellow                                        260          5-Cl                                                                                      ##STR135##                                                                              yellow                                        261          5-Cl      C.sub.4 H.sub.9                                                                          yellow                                        262          5-Br      CH.sub.3  yellow                                        263          5-Br      C.sub.2 H.sub.5                                                                          yellow                                        264          5-Br      C.sub.3 H.sub.7                                                                          yellow                                        265          5-Br                                                                                      ##STR136##                                                                              yellow                                        266          5-Br      C.sub.4 H.sub.9                                                                          yellow                                        267          5-NO.sub.2                                                                               H         yellow                                        268          5-NO.sub.2                                                                               CH.sub.3  yellow                                        269          5-NO.sub.2                                                                               C.sub.2 H.sub.5                                                                          yellow                                        270          5-NO.sub.2                                                                               C.sub.3 H.sub.7                                                                          yellow                                        271          5-NO.sub.2                                                                                ##STR137##                                                                              yellow                                        272          5-NO.sub.2                                                                               C.sub.4 H.sub.9                                                                          yellow                                        273        3,5-Br.sub.2                                                                               H         yellow                                        274        3,5-Br.sub.2                                                                               CH.sub.3  yellow                                        275        3,5-Br.sub.2                                                                               C.sub.2 H.sub.5                                                                          yellow                                        276        3,5-Br.sub.2                                                                               C.sub.3 H.sub.7                                                                          yellow                                        277        3,5-Br.sub.2                                                                                ##STR138##                                                                              yellow                                        278        3,5-Br.sub.2                                                                               C.sub.4 H.sub.9                                                                          yellow                                        279        3,5-Cl.sub.2                                                                               H         yellow                                        280        3,5-Cl.sub.2                                                                               CH.sub.3  yellow                                        281        3,5-Cl.sub.2                                                                               C.sub.2 H.sub.5                                                                          yellow                                        282        3,5-Cl.sub.2                                                                               C.sub.3 H.sub.7                                                                          yellow                                        283        3,5-Cl.sub.2                                                                                ##STR139##                                                                              yellow                                        284        3,5-Cl.sub.2                                                                               C.sub.4 H.sub.9                                                                          yellow                                        285          3-Cl, 5-Br                                                                               H         yellow                                        286          3-Cl, 5-Br                                                                               CH.sub.3  yellow                                        287          3-Cl, 5-Br                                                                               C.sub.2 H.sub.5                                                                          yellow                                        288          3-Cl, 5-Br                                                                               C.sub.3 H.sub.7                                                                          yellow                                        289          3-Cl, 5-Br                                                                                ##STR140##                                                                              yellow                                        290          3-Cl, 5-Br                                                                               C.sub.4 H.sub.9                                                                          yellow                                        291          3-Br, 5-Cl                                                                               H         yellow                                        292          3-Br, 5-Cl                                                                               CH.sub.3  yellow                                        293          3-Br, 5-Cl                                                                               C.sub.2 H.sub.5                                                                          yellow                                        294          3-Br, 5-Cl                                                                               C.sub.3 H.sub.7                                                                          yellow                                        295          3-Br, 5-Cl                                                                                ##STR141##                                                                              yellow                                        296          3-Br, 5-Cl                                                                               C.sub.4 H.sub.9                                                                          yellow                                        297          6-Cl      H         yellow                                        298          6-Cl      CH.sub.3  yellow                                        299          6-Cl      C.sub.2 H.sub.5                                                                          yellow                                        300          6-Cl      C.sub.3 H.sub.7                                                                          yellow                                        301          6-Cl                                                                                      ##STR142##                                                                              yellow                                        302          6-Cl      C.sub.4 H.sub.9                                                                          yellow                                        ______________________________________                                    

EXAMPLE 303

162 parts of dianthranilic acid piperazide in 500 parts of water are stirred for a few hours with the addition of 0.5 part of a sodium alkylnaphthalenesulfonate. 275 ml of concentrated HCl are added, after which stirring is continued for 1/2 hour, ice is then added and diazotization is effected with 310 parts by volume of 23 percent strength aqueous sodium nitrite solution at from 0° to 5° C. After 11/2 hours, excess nitrite is destroyed with amidosulfonic acid and the solution is filtered.

41.4 parts of 3-cyano-6-hydroxy-1,4-dimethylpyrid-2-one are dissolved in a mixture of 100 parts of 2N sodium hydroxide solution and 600 parts of water with heating. 500 parts of a 10 percent strength aqueous rosin solution which has been rendered alkaline with sodium hydroxide are added at room temperature, and a solution of 2.9 parts of 3-cyano-6-hydroxy-4-methyl-1-(γ-trimethylammoniumpropyl)pyrid-2-one in 10 parts of glacial acetic acid is added dropwise. The diazonium salt solution is run into 85% of this suspension, while stirring thoroughly, and the mixture is titrated with the remaining 15% of the coupling component in the course of 1/2 hour until a small excess of diazo component is present. After 10 minutes, the pH is brought to 12 with 50 percent strength aqueous sodium hydroxide solution, stirring is continued for 5 minutes and the mixture is acidified with 30 parts of formic acid. The pH is then brought to 9 with sodium hydroxide solution and the mixture is stirred for 4 hours at 98° C. The pH is then brought to 5 with dilute hydrochloric acid, the mixture is cooled to 50° C. and the product is filtered off under suction, washed salt-free with water and dried at 50° C. to give 117 parts of a yellow pigment. The principal component is of the formula ##STR143## and the secondary components are of the formulae ##STR144##

The secondary coupling components stated in the table below can be used in a similar manner in the preparation of the pigments, also in combination with other principal coupling components. However, it is also possible to prepare the pure colorants DIAP→(secondary coupling component 1, secondary coupling component 2) and to add them before or after the principal coupling reaction which leads to the pigment.

    ______________________________________                                          ##STR145##                                                                    Example No. R                 Color                                            ______________________________________                                         304         C.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                                yellow                                           305         C.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                         yellow                                           306                                                                                         ##STR146##       yellow                                           307         C.sub.2 H.sub.4 N(C.sub.4 H.sub.9).sub.2                                                         yellow                                           308                                                                                         ##STR147##       yellow                                           309         C.sub.3 H.sub.6 N(CH.sub.3).sub.2                                                                yellow                                           310         C.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2                                                         yellow                                           311         C.sub.3 H.sub.6 N(C.sub.3 H.sub.7).sub.2                                                         yellow                                           312         C.sub.3 H.sub.6 N(CH(CH.sub.3).sub.2).sub.2                                                      yellow                                           313         C.sub.3 H.sub.6 N(C.sub.4 H.sub.9).sub.2                                                         yellow                                           314                                                                                         ##STR148##       yellow                                           315                                                                                         ##STR149##       yellow                                           316                                                                                         ##STR150##       yellow                                           317                                                                                         ##STR151##       yellow                                           318                                                                                         ##STR152##       yellow                                           319                                                                                         ##STR153##       yellow                                           320         C.sub.3 H.sub.6 NHC.sub.12 H.sub.25                                                              yellow                                           321         C.sub.3 H.sub.6 NHkokos                                                                          yellow                                                       (C.sub.8, C.sub.10, C.sub.12, C.sub.12, C.sub.16,                                                yellow18)                                        322         C.sub.3 H.sub.6 NHTalgfett                                                                       yellow                                                       (C.sub.14, C.sub.16, C.sub.18)                                     323         C.sub.3 H.sub.6 NHOleyl                                                                          yellow                                                       (C.sub.14, C.sub.16, C.sub.18)                                     324                                                                                         ##STR154##       yellow                                           325                                                                                         ##STR155##       yellow                                           326                                                                                         ##STR156##       yellow                                           327                                                                                         ##STR157##       yellow                                           328                                                                                         ##STR158##                                                        ______________________________________                                    

EXAMPLES OF USE

(a) Surface coating

10 parts of the colorant obtained as described in Example 20 and 95 parts of a baking finish mixture containing 70% of coconut alkyd resin (60% strength solution in xylene) and 30% of melamine resin (roughly 55% strength solution in butanol/xylene) are milled in an attrition mill. After application and baking for 30 minutes at 120° C., red full-shade coatings possessing good depth and lightfastness are obtained. If titanium dioxide is added, red white reductions are produced.

If the colorants described in Examples 1-302 are used, some of the coatings obtained have good depth.

(b) Plastic (soft PVC)

0.05 part of a colorant obtained as described in Example 99 and 50 parts of a mixture of 65 parts of PVC powder, 36 parts of di-ethylhexyl phthalate and 2 parts of dibutyltin bis-(hexylthioglycolate) are homogenized on a roll mill at 150°-160° C. for about 8 minutes, milled to give hides, and polished on a calender. Yellow sheets having good lightfastness and fastness to plasticizers are obtained. If titanium oxide is added during incorporation, yellow reductions of good depth are obtained.

If the pigment dyes obtained as described in Examples 1-302 are used, similar colorations are obtained.

(c) Printing ink

8 parts of the pigment dye obtained as described in Example 1, 40 parts of a rosin modified with phenol/formaldehyde, and from 55 to 65 parts of toluene are mixed thoroughly in a dispersing unit. A yellow toluene-based gravure printing ink is obtained. The prints obtained with this ink possess a good depth.

If the colorants of Examples 2-302 are used, similar results are obtained. 

We claim:
 1. A sulfo-free compound of the formula ##STR159## where R is hydrogen or C₁ -C₄ -alkyl andK¹ and K² independently of one another are a radical of a coupling component, and the rings A and B are unsubstituted, or are monosubstituted or polysubstituted by fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, ethyl, acetyl, benzoyl, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOCH(CH₃)₂, COOC₄ H₉, COOC₆ H₅, COOC₆ H₁₃, COOC₈ H₁₇, COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOCH₂ C₆ H₅, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₃ H₇, CONHC₄ H₉, CONHCH(CH₃)₂, CONHCH₂ C₆ H₅, CONHC₆ H₅, CONHC₆ H₄ Cl, CONHC₆ H₃ Cl₂, CONHC₆ H₂ Cl₃, CONHC₆ H₄ Br, CONHC₆ HL₄ OCH₃, CONHC₆ H₄ CH₃, CONHC₆ H₄ OC₂ H₅, CONHC₆ H₃ Cl(OCH₃), CONHC₆ H₄ NHCOCH.sub. 3, CONHC₆ H₄ NHCOC₆ H₅, CONHNHCOC₆ H₅, CONHNHCOC₆ H₄ Cl, CONHNHCOC₆ H₄ CH₃, SO₂ NH₂, SO₂ NHCH₃, SO₂ NHC₂ H₅, SO₂ NHC₃ H₇, SO₂ NHC₄ H₉, SO₂ NHCH(CH₃)₂, SO₂ NHCH₂ C₆ H₅, SO₂ NHC₆ H₅, SO₂ NHC₆ H₄ Cl, SO₂ NHC₆ H₃ Cl₂, SO₂ NHC₆ H₂ Cl₃, SO₂ NHC₆ H₄ Br, SO₂ NHC₆ H₄ OCH₃, SO₂ NHC₆ H₄ CH₃, SO₂ NHC₆ H₄ OC₂ H₅, SO₂ NHC₆ H₃ Cl(OCH₃), SO₂ NHC₆ H₄ NHCOCH₃, SO₂ NHC₆ H₄ NHCOC₆ H₅, SO₂ NHNHCOC₆ H₅, SO₂ NHNHCOC₆ H₄ Cl, SO₂ NHNHCOC₆ H₄ CH₃, SO₂ OC₆ H₅, SO₂ OC₆ H₄ CH₃, SO₂ OC₆ H₄ Cl, SO₂ OC₆ H₄ Br, SO₂ OC₆ H₄ OCH₃, SO₂ OC.sub. 6 H₄ NHCOCH₃, SO₂ OC₆ H₃ Cl₂, SO₂ C₆ H₅, SO₂ C₆ H₄ Cl, NHCOCH₃, NHCOC₂ H₅, NHCOC₆ H₅, NHCONH₂, NHCON(CH₃)₂, NHCONHC₆ H₅, C₁ -C₄ -alkylsulfonyl or cyano.
 2. A compound as claimed in claim 1 of the formula ##STR160## where K³ and K⁴ independently of one another are each a radical of the formulae ##STR161## where R¹ is C₁ -C₄ -alkoxy, phenoxy which is unsubstituted or is substituted by chlorine, or arylamino which is unsubstituted or is substituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl, or sulfamyl;R² is aryl which is unsubstituted or is substituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl, or sulfamyl; R³ is hydrogen, methyl, carboxyl, C₁ -C₈ -alkoxycarbonyl, carbamyl or the substituents stated for R² ; R⁴ is hydrogen or the substituents stated for R², R⁵ is hydrogen or C₁ -C₁₃ -alkyl; R⁶ is hydrogen, hydroxyl, amino or C₁ -C₄ -alkyl; R⁷ is hydrogen, cyano, carbamyl, acetyl or benzoyl; R⁸ and R¹³ independently of one another are each hydrogen, C₁ -C₂₂ alkyl which is unsubstituted or substituted by hydroxy, methoxy, cyano, carbomethoxy, carboethoxy, acetoxy, ethoxycarbonyl, acetylamino, phenoxycarbonyloxy, phenylaminocarbonyloxy, butylaminocarbonyloxy, phenyl, or sulfo; phenyl or benzyl; R⁹, R¹⁰ and R¹¹ independently of one another are each hydrogen or C₁ -C₈ alkyl which is unsubstituted, or C₂ -C₆ -alkyl which is substituted by hydroxyl, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy, phenoxyethoxy or benzyloxy; cyclohexyl, or phenyl, or R¹⁰ and R¹¹ together with the nitrogen form a 5-membered or 6-membered heterocyclic ring; R¹² and R¹⁷ independently of one another are each oxygen, iminio or cyanoimino; R¹⁴ is a radical R⁸, amino, C₁ -C₈ alkanoylamino, or benzoylamino which is unsubstituted or is monosubstituted or disubstituted by hydroxyl, chlorine, methyl, methoxy, acetylamino, nitro or amino; R¹⁵ is hydrogen or phenyl which is unsubstituted or is monosubstituted, disubstituted or trisubstituted by chloro, bromo, methoxy or methyl; R¹⁶ is hydroxyl, methyl, a carboxylic C₁ -C₂ -alkyl ester group, a member selected from the group consisting of NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇, NHCOC₆ H₅, NHCOC₆ H₄ Cl, NHCOC₆ H₃ Cl₂, NHCOC₆ H₄ Br, NHCOC₆ H₄ OCH₃, NHCONH₂, NHCONHC₆ H₅ and NHCOCONHC₆ H₅ ; or a radical R¹⁵, and the ring A is unsubstituted or is substituted in the stated manner and the phenylene radicals A are unsubstituted or are monosubstituted or polysubstituted by chlorine, bromine or nitro, the substituents being identical or different in the case of polysubstitution.
 3. A compound as claimed in claim 2, whereinR¹ is NHC₆ H₅ which is unsubstituted or is monosubstituted or polysubstituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl or sulfamyl, the substituents being identical or different in the case of polysubstitution; R² is phenyl which is unsubstituted or is monosubstituted or polysubstituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl or sulfamyl, the substituents being identical or different in the case of polysubstitution; R³ is hydrogen, methyl, C₁ -C₄ -alkoxycarbonyl, carbamyl, C₁ -C₄ -alkylaminocarbonyl or the radicals given for R² ; R⁴ is hydrogen or the radicals given for R² ; R⁵ is hydrogen or C₁ -C₈ -alkyl; R⁶ is hydrogen, cyano, carbamyl, acetyl or benzoyl; R⁸ and R¹³ independently of one another are each hydrogen, C₁ -C₂₂ alkyl, benzyl or a radical R² ; R⁹, R¹⁰ and R¹¹ independently of one another are each hydrogen, C₁ -C₈ alkyl, cyclohexyl, benzyl or a radical R², or R¹⁰ and R¹¹ together with the nitrogen form a 5-membered or 6-membered heterocyclic ring; R¹² and R¹⁷ independently of one another are each oxygen, imino or cyanoimino; R¹⁴ is a radical R⁸ or C₁ -C₈ alkanoylamino or benzoylamino which is unsubstituted or is substituted by hydroxyl, chlorine, methyl, methoxy, acetylamino, nitro or amino; R¹⁵ is hydrogen or a radical R² and R¹⁶ is methyl or a radical R². 